Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
  • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups

Definitions

• the present invention relates to an improved process for the manufacture of 2-methyl-2-hepten-6-one by reacting an alkyl acetoacetate with 2-methyl-3-buten-2-ol at an elevated temperature in the presence of an organic aluminum compound such as aluminum trialcoholate, aluminum triacetoacetate, aluminum alkyl acetoacetate or aluminum triaryloxylate.
• an organic aluminum compound such as aluminum trialcoholate, aluminum triacetoacetate, aluminum alkyl acetoacetate or aluminum triaryloxylate.
• German Pat. No. 1,068,696 discloses the preparation of 2-methyl-2-hepten-6-one by passing 2-methyl-3-buten-2-ol into a reaction mixture which has been preheated to 160°-250° C.
• the conditions required according to the invention may be achieved in a simple manner by, for example, introducing, into a reaction vessel possessing a fractionating column, a solution of the aluminum compound in the alkyl acetoacetate, in a mixture of the alkyl acetoacetate and small amounts of methylbutenol, in a high-boiling inert solvent, e.g., tetralin or dimethylformamide, or in a high-boiling weak base, e.g., quinoline or dimethylaniline, or in a small amount of the reaction product 2-methyl-2-hepten-6-one, and introducing methylbutenol and the alkyl acetoacetate into this solution at the reaction temperature, at the rate at which the reaction progresses, in a molar ratio such that within 2 hours, preferably within 1 hour, a molar excess of methylbutenol is present in the reactiion mixture, whilst ensuring that the alcohol formed in the reaction distill
• the progress of the reaction may be followed by measuring the carbon dioxide evolved and/or the amount of alkanol eliminated from the alkyl acetoacetate.
• the concentration of the alkyl acetoacetate in the reaction mixture can be determined by analysis by gas chromatography.
• the reaction is carried out in such a way that virtually no methylbutenol acetoacetate is detectable in the mixture; this is essential if the high yields according to the invention are to be achieved.
• the amount of methylbutenol to be employed is preferably at least 1.1 moles per mole of alkyl acetoacetate. It depends on the separating capacity of the fractionating column. The better is the latter, the lower are the amounts of methylbutenol which are lost in the course of distilling off the alcohol. In general, from about 1.2 to 1.5 moles of methylbutenol are required per mole of alkyl acetoacetate.
• Suitable organic aluminum compounds for the process according to the invention are those of the general formula ##STR1## where R 1 and R 2 are alkyl or alkoxy of 1 to 4 carbon atoms, preferably methyl or ethyl, R 3 is alkyl of 1 to 4 carbon atoms and n is 0, 1, 2 or 3. Accordingly, these compounds are lower aluminum trialcoholates, e.g., aluminum trimethylate, aluminum triethylate, aluminum triisopropylate and aluminum tri-sec.-butylate, and compounds which are formed, with elimination of alcohol, on reacting the said aluminum trialcoholates with stoichiometric amounts of an acetylacetonate, alkyl acetoacetate or alkyl malonate.
• R 1 and R 2 are alkyl or alkoxy of 1 to 4 carbon atoms, preferably methyl or ethyl
• R 3 is alkyl of 1 to 4 carbon atoms
• n is 0, 1, 2 or 3.
• these compounds are lower aluminum trial
• Examples are aluminum triacetoacetate, aluminum triacetylacetonate, aluminum monoacetoacetate diethylate, aluminum diacetoacetate monoethylate, aluminum monoacetoacetate diisopropylate and aluminum diacetoacetate monoisopropylate.
• aluminum triaryloxylate means an aluminum salt of an aromatic hydroxylic compound, e.g. aluminum triphenolate, the aluminum tricresolates, the aluminum trixylenolates and the aluminum trinaphtholates, the aryl radicals of which may or may not be substituted by lower alkyl or alkoxy, i.e., alkylor alkoxy of 1 to 4 carbon atoms, hydroxyl or phenyl. It is particularly advantageous to use aluminum triphenolate, which is relatively easily accessible.
• the amount of the aluminum compound is generally so chosen that the concentration in the reaction mixture does not fall below 0.05% by weight of Al and does not exceed 6% by weight of Al at the start of the reaction. In general, from 1 to 5% by weight, based on alkyl acetoacetate to be converted, of the aluminum compound are required. In the case of aluminum triisopropylate, the preferred compound, the amounts required are, for example, from about 1 to 3% by weight of Al, based on alkyl acetoacetate to be converted, are required.
• the reaction may be carried out continuously or batchwise and is advantageously carried out under atmospheric pressure.
• the amount of methylbutenol to be employed can be reduced substantially by working under superatmospheric pressure. Furthermore, such pressures, of from 1 to 10 atmospheres gauge, allow the reaction temperature to be raised to 170°-180° C. The batch time is substantially reduced and hence the capacity of the plant is substantially increased. At the shorter reaction times achieved, the activity of the aluminum alcoholate suffers less.
• the reaction mixtures are advantageously worked up by distillation; first, the methylbutenol and low-boiling by-products are separated off and thereafter the methylheptenone is subjected to fractional distillation. Any desired degree of purity is achievable in this way. If the methylheptenone obtained is to be employed as a solvent for the reaction according to the invention, prior purification by distillation is not necessary. Instead, the crude methylheptenone, containing at least 85% by weight of the said compound, can be employed. The residue obtained contains the aluminum compound plus any high-boiling solvent. This residue may be used for subsequent reaction batches.
• 2-methyl-2-hepten-6-one is obtained in the unexpextedly high yields of more than 90% of theory. Accordingly, the measures according to the invention prevent the formation of resinified products, usually encountered in this reaction, the formation of substantial amounts of acetone and isoprene, and the formation of prenyl acetoacetate, which can only be converted incompletely to methylheptenone.
• 2-Methyl-2-hepten-6-one is a valuable intermediate for the manufacture of scents and vitamins, e.g., vitamin A.
• the composition of the reaction mixture is as shown in the Table (analysis by gas chromatography: OV17 column material, temperature 100° C., followed by 130° C.).
• the yield of methylheptenone is 88.6% of theory, based on methylbutenol converted, and 87.7%, based on alkyl acetoacetate employed.
• the composition of the reaction mixture is as shown in the Table (analysis by gas chromatography: OV17 column material, temperature 100° C., followed by 130° C.).
• the composition of the reaction mixture is as shown in the Table (analysis by gas chromatography: OV17 column material, temperature 100° C., followed by 130° C.).
• the composition of the reaction mixture is as shown in the Table (analysis by gas chromatography: OV17 column material, temperature 100° C., followed by 130° C.).
• a mixture of 15 g of aluminum triphenolate, 78 g (0.67 mole) of methyl acetoacetate and 72 g (0.84 mole) of 2-methyl-3-buten-2-ol is heated at 145° C. in a reaction vessel connected to a distillation column. In the course of 9.5 hours, a mixture of 386 g (3.33 moles) of methyl acetoacetate and 358 g (4.16 moles) of 2-methyl-3-buten-2-ol is added uniformly to the solution obtained. The methanol formed is distilled off continuously.
• the composition of the reaction mixture is as shown in the Table (analysis by gas chromatography: OV17 column material, temperature 100° C., followed by 130° C.).
• the composition of the reaction mixture is as shown in the Table (analysis by gas chromatography: OV17 column material, temperature 100° C., followed by 130° C.).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Fats And Perfumes (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=25771167

Family Applications (1)

Country Status (7)

Cited By (6)

Families Citing this family (3)

Citations (5)

Family Cites Families (4)

• 1977
  • 1977-10-31 IT IT29226/77A patent/IT1089011B/it active
  • 1977-11-03 US US05/848,211 patent/US4173588A/en not_active Expired - Lifetime
  • 1977-11-09 NL NL7712353A patent/NL7712353A/xx not_active Application Discontinuation
  • 1977-11-17 CH CH1408177A patent/CH634287A5/de not_active IP Right Cessation
  • 1977-11-18 FR FR7734688A patent/FR2371411A1/fr active Granted
  • 1977-11-18 GB GB48069/77A patent/GB1589359A/en not_active Expired
  • 1977-11-21 JP JP13900977A patent/JPS5365813A/ja active Granted

Patent Citations (5)

Also Published As

Similar Documents